EP0032639B1 - Procédé pour l'oxydation de lupulones en hulupones - Google Patents

Procédé pour l'oxydation de lupulones en hulupones Download PDF

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Publication number
EP0032639B1
EP0032639B1 EP19800304773 EP80304773A EP0032639B1 EP 0032639 B1 EP0032639 B1 EP 0032639B1 EP 19800304773 EP19800304773 EP 19800304773 EP 80304773 A EP80304773 A EP 80304773A EP 0032639 B1 EP0032639 B1 EP 0032639B1
Authority
EP
European Patent Office
Prior art keywords
sodium
potassium
hulupones
lupulones
reaction medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19800304773
Other languages
German (de)
English (en)
Other versions
EP0032639A3 (en
EP0032639A2 (fr
Inventor
Michael Torrey Wuesthoff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pfizer Inc
Original Assignee
Pfizer Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pfizer Inc filed Critical Pfizer Inc
Priority to AT80304773T priority Critical patent/ATE13445T1/de
Publication of EP0032639A2 publication Critical patent/EP0032639A2/fr
Publication of EP0032639A3 publication Critical patent/EP0032639A3/en
Application granted granted Critical
Publication of EP0032639B1 publication Critical patent/EP0032639B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C3/00—Treatment of hops
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C9/00—Methods specially adapted for the making of beerwort
    • C12C9/02—Beerwort treatment; Boiling with hops; Hop extraction
    • C12C9/025—Preparation of hop extracts; Isomerisation of these extracts; Treatment of beerwort with these extracts; Surrogates of the hop

Definitions

  • This invention relates to an improved method for winning bitter substances from hops and rendering them suitable for use as bittering agents in beer making. More particularly, it relates to an improved process for converting the so-called beta-acid component of the hop resins from hop cones, which are normally discarded in conventional brewing processes, into a form which can be used satisfactorily as a bittering agent in beer making. This process is an oxygenation reaction, in which lupulones are converted into hulupones.
  • lupulones is well known in the art to include not only lupulone itself, but other compounds present in the beta-acid component, including colupulone.
  • hulupones is well known in the art to include not only hulupone itself, but other compounds present in oxidised lupulones, including cohulupone.
  • This invention provides an improvement in the process for producing hulupones by oxidation of lupulones, using an oxygen-containing gas, in a substantially aqueous reaction medium rendered alkaline by the addition of an alkalyzing agent.
  • Said improvement consists of carrying out the process using conditions under which the hulupone product is precipitated directly out of the reaction medium as the sodium or potassium salt. Precipitation is caused to occur quite conveniently by using a sodium-ion or potassium-ion containing alkalyzing agent, and running the process with a high initial concentration of lupulones. The same effect, i.e.
  • the sodium or potassium ions can be derived from the alkalyzing agent, or from a supplementary sodium ion or potassium ion source. Additionally, when a high sodium ion or potassium ion concentration is used, the sodium or potassium ions can be derived partly from the alkalyzing agent and partly from a supplementary sodium ion or potassium ion source.
  • Hops have been used in the brewing industry for hundreds of years, on account of their content of bitter substances.
  • the hop cones are boiled with sweet wort in a copper kettle for about one to two hours, and then the wort is filtered and allowed to cool.
  • the hop resins the so-called alpha-acids or humulones
  • beta-acids or lupulones the so-called beta-acids or lupulones
  • the conversion can be carried out using oxygen in the presence of sodium sulfite in alcoholic solution, or with sodium peroxydisulfate in ethanol.
  • lupulone-containing substances were dissolved in trichloroethylene and treated with oxygen.
  • the simplest and most convenient method of carrying out this conversion comprises dissolving lupulone-containing material in a substantially aqueous reaction medium, at an alkaline pH, and treating this solution with oxygen gas, optionally in the presence of a catalyst.
  • this method has been used successfully, it suffers from disadvantages, and the purpose of the present invention is to provide an improvement in this process.
  • Said improvement comprises conducting the reaction using conditions under which substantially all of the hulupone product precipitates directly from the reaction medium as a sodium or a potassium salt. This offers the unexpected advantage of providing hulupones of higher purity than has been possible hitherto.
  • the expedient of causing the products to precipitate directly from the reaction medium avoids the problem of overoxidation, a common problem with the prior art processes. Additionally, by causing the products to precipitate directly from the reaction medium, a purer product is obtained, since impurities are retained in solution.
  • the present invention offers the further advantage of simplified isolation of products. Whereas prior art processes require that the reaction mixture be acidified and extracted with a water-immiscible organic solvent, or the hulupones precipitated from the reaction mixture after oxidation, as a separate step, the process of the present invention allows direct isolation of the hulupone salts from the reaction mixture.
  • lupulones or lupulone-containing material
  • a substantially aqueous solution at a pH in the range from about 10 to about 14, preferably 13 to 14.
  • This solution is then contacted with an oxygen-containing gas, at a temperature in the range from about 25 to about 100°C, preferably 50-90°C. It is possible simply to bubble the oxygen-containing gas through the reaction medium, with good agitation; however, particularly when working on a large scale, it is usually more convenient to use a sealed.
  • reaction vessel containing the lupulone solution and substantially pure oxygen gas Under these conditions the pressure inside the reaction vessel is usually in the range from about 10 to about 120 psig, with a pressure of about 50 to about 100 psig being preferred.
  • the pH value of 10 to 14 is achieved by adding an alkalyzing agent to the reaction medium, and a wide variety of alkalyzing agents can be used, including both organic and inorganic types.
  • the major requirements for the alkalyzing agent are that the pKa of its conjugate acid must be sufficiently high that a pH of 10 to 14 can be achieved, and the alkalyzing agent must not adversely interact with either the lupulone reactant or the hulupone product.
  • organic alkalyzing agents are tertiary amines, such as triethylamine or N-methylpiperidine
  • examples of inorganic alkalyzing agents are the hydroxides, carbonates and phosphates of the alkali metals, e.g. the hydroxides, carbonates and phosphates of sodium and potassium.
  • Sodium hydroxide and potassium hydroxide are particularly useful agents.
  • oxygen-containing gas refers to pure oxygen and to oxygen diluted with inert diluents such as nitrogen and argon, and it includes air.
  • Reaction times vary according to a variety of factors, such as the reaction temperature, the concentration of the lupulone solution and the partial pressure of the oxygen. However, at a temperature of 50 to 90°C, and working in a sealed vessel with pure oxygen at a pressure of about 50 to 100 psig, with lupulone concentrations of about 5 to 30% on a weight per volume basis, reaction times of about 0.5 to 2 hours are commonly used. In any event, it is usually preferable to monitor the reaction by following oxygen uptake. Usually the reaction is stopped when from about 100 to about 170 mole percent of oxygen has been absorbed, based on the initial lupulone starting material.
  • the process of this invention is carried out under conditions which cause the hulupone product to precipitate as its sodium or potassium salt.
  • This is most simply achieved by using a sodium-ion or potassium-ion containing alkalyzing agent and working at higher initial concentrations of lupulones than have been used hitherto.
  • a sodium-ion or potassium-ion containing alkalyzing agent is used, substantially all the hulupones (i.e. at least 85%) will precipitate if an initial concentration of lupulones of between 15 and 30 percent, on a weight per volume basis, is used.
  • the preferred initial lupulone concentration is 20 to 25 percent.
  • the process of this invention can also be carried out at initial lupulone concentrations of less than 15 percent.
  • the hulupone product is induced to precipitate (as its sodium or potassium salt) by conducting the reaction in the presence of a large excess of a cation selected from the group consisting of sodium and potassium. Effectively, this depresses the solubility of the sodium or potassium salt of the hulupone, and thus causes it to precipitate.
  • initial concentrations of lupulones of as low as about 3 percent can be oxidized efficiently.
  • the amount of excess sodium or potassium ion varies with the initial concentration of the lupulones, but total concentrations of sodium ions from about 0.5 to about 3.0 molar, and total concentrations of potassium ions from about 1.0 to about 5.0 molar, are normally used. Clearly, cation concentrations from the higher ends of these ranges are used when the initial concentration of lupulones is low, while cation concentrations from the low ends of these ranges are used when the initial concentration of lupulone is high.
  • sodium-ion containing or potassium-ion containing alkalyzing agent In order to achieve the excess sodium ion or potassium ion levels, it is possible simply to use an excess of a sodium-ion containing or potassium-ion containing alkalyzing agent.
  • a sodium-ion concentration of 0.5 to 3.0 molar sufficient sodium-ion containing alkalyzing agent, such as sodium hydroxide, sodium carbonate or sodium phosphate, or mixture thereof, is added to give the requisite concentration.
  • potassium ion concentration of 1.0 to 5.0 molar sufficient potassium-ion containing alkalyzing agent, such as potassium hydroxide, potassium carbonate or potassium phosphate, or mixture thereof, is added to give the requisite concentration.
  • supplementary cation sources can be used.
  • the major requirements for such an agent are that it liberates ionic sodium or potassium on dissolution in water, and that the counterion thus liberated does not adversely affect the lupulones or the hulupones.
  • Sodium or potassium salts of both inorganic and organic acids can be used; however, for reasons of accessibility and economy, convenient supplementary sodium ion sources are sodium chloride, sodium sulfate and sodium acetate, and convenient supplementary potassium ion sources are potassium chloride, potassium sulfate and potassium acetate.
  • the process of this invention represents an improvement over known processes for oxidizing lupulones to hulupones, with oxygen gas, in a substantially aqueous, alkaline medium. It is known that such processes can be carried out in the presence of a wide variety of catalysts, and it is to be understood that the improvement disclosed and claimed herein applies equally well to catalyzed as well as uncatalyzed processes. It is known that both homogeneous and heterogeneous catalysts can be used and that heterogeneous catalysts can be used in both supported and unsupported forms. The improvement of this invention applies in all situations. In particular, the improvement applies to the processes disclosed in United States Patents Nos. 4,013,721 and 2,652,333, and Belgian Patent No. 805,280.
  • the hulupone product obtained from the process of this invention is readily isolated by conventional techniques.
  • the product can be recovered simply by filtration, and it can be purified by known methods for hulupone compounds, if desired.
  • a simple method of purification which is often used involves dissolution of the hulupone in methanol, filtration of the methanol solution and removal of the methanol by solvent evaporation.
  • the product was assayed by ultraviolet spectroscopy, according to standard techniques.
  • the assay indicated that the crude product contained 50% hulupones, which corresponds to a 40% yield.
  • HPLC high-pressure liquid chromatography
  • Example 3 The procedure of Example 3 is repeated, except that the sodium sulfate is replaced by 76 mmoles of sodium chloride and sodium acetate, respectively. This affords, in each case, cohulupone sodium salt.
  • Example 5 The procedure of Example 5 is repeated, except that the potassium sulfate is replaced by 90 mmoles of potassium chloride and potassium acetate, respectively. This affords, in each case, cohulupone potassium salt.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Food Science & Technology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (3)

1. Procédé d'oxydation de lupulones en hulupones, en utilisant un gaz contenant de l'oxygène, dans un milieu réactionnel principalement aqueux rendu alcalin au moyen d'un agent alcalinisant, à une température comprise dans l'intervalle de 25 à 100°C, en utilisant une concentration initiale en lupulones d'au moins 3%, et en recueillant les hulupones par précipitation, caractérisé par le fait que:
(i) l'opération d'oxydation est conduite dans un milieu réactionnel auquel des ions sodium ont été ajoutés pour qu'il y ait une concentration molaire en ions sodium dans l'intervalle de 0,5 à 3,0 suffisante pour provoquer la précipitation de la quasi-totalité des hulupones directement dans le milieu réactionnel sous la forme du sel de sodium, ou bien des ions potassium ont été ajoutés pour qu'il y ait une concentration molaire en ions potassium dans l'intervalle de 1,0 à 5,0 suffisante pour provoquer la précipitation de la quasi-totalité des hulupones directement dans le milieu réactionnel sous la forme du sel de potassium; et
(ii) les hulupones sont ensuite recueillies dans le milieu réactionnel sous la forme du sel de sodium ou du sel de potassium.
2. Procédé suivant la revendication 1, caractérisé en ce qu'il est mis en oeuvre dans un milieu réactionnel auquel un agent alcalinisant choisi entre l'hydroxyde de sodium, le carbonate de sodium et le phosphate de sodium a été ajouté de manière qu'il y ait une concentration molaire en ions sodium dans l'intervalle de 0,5 à 3,0.
3. Procédé suivant la revendication 2, caractérisé en ce que l'agent alcalinisant est l'hydroxyde de sodium.
EP19800304773 1980-01-07 1980-12-31 Procédé pour l'oxydation de lupulones en hulupones Expired EP0032639B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80304773T ATE13445T1 (de) 1980-01-07 1980-12-31 Verfahren zur oxidation von lupulonen zu huluponen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11041480A 1980-01-07 1980-01-07
US15568680A 1980-06-02 1980-06-02
US155686 1980-06-02
US110414 1987-10-20

Publications (3)

Publication Number Publication Date
EP0032639A2 EP0032639A2 (fr) 1981-07-29
EP0032639A3 EP0032639A3 (en) 1982-03-31
EP0032639B1 true EP0032639B1 (fr) 1985-05-22

Family

ID=26808004

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19800304773 Expired EP0032639B1 (fr) 1980-01-07 1980-12-31 Procédé pour l'oxydation de lupulones en hulupones

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EP (1) EP0032639B1 (fr)
AU (1) AU521674B2 (fr)
DE (1) DE3070685D1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK163185A (da) * 1984-04-12 1985-10-13 Scottish & Newcastle Breweries Fremgangsmaade til fremstilling af oel med foroeget bitterhed
US5583262A (en) * 1994-11-10 1996-12-10 Maye; John P. Solid salts of hop acids
US20060287554A1 (en) * 2005-06-21 2006-12-21 Madsen Kevin K Process for producing inorganic salts of hop acids
CA2960820C (fr) * 2014-09-12 2023-04-04 Ifast Nv Procede de production de bieres stockees, offertes, servies ou consommees dans des bouteilles laissant passer la lumiere uv-vis ayant une sensibilite reduite, en particulier aucun e sensibilite, a la degradation de l'odeur forte et nauseabonde du thiol apres exposition a la lumiere solaire ou a d'autres sources de lumiere uv et/ou vis, et bieres ainsi produ
CN110637081B (zh) * 2017-04-06 2024-01-09 Ifast 公众有限责任公司 希鲁酮及希鲁酮产品的生产

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977953A (en) * 1972-04-10 1976-08-31 Atlantic Research Institute Ltd. Process for the production of hulupones
DE2217134A1 (de) * 1972-04-10 1973-10-31 Atlantic Res Inst Neue oxydationsprodukte von lupulon
AU474292B2 (en) * 1972-09-13 1976-07-15 Atlantic Research Institute Ltd Process for the catalytic oxidation of lupulones into hulupones
DE2348058A1 (de) * 1972-09-25 1974-04-04 Watney Mann Ltd Verfahren zur gewinnung von huluponen durch oxydation von lupulonen

Also Published As

Publication number Publication date
DE3070685D1 (en) 1985-06-27
AU521674B2 (en) 1982-04-22
EP0032639A3 (en) 1982-03-31
EP0032639A2 (fr) 1981-07-29
AU6600581A (en) 1981-07-16

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